CN109311698A - Ternary precursor material and preparation method thereof - Google Patents
Ternary precursor material and preparation method thereof Download PDFInfo
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- CN109311698A CN109311698A CN201780035059.6A CN201780035059A CN109311698A CN 109311698 A CN109311698 A CN 109311698A CN 201780035059 A CN201780035059 A CN 201780035059A CN 109311698 A CN109311698 A CN 109311698A
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- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract
The present invention provides a kind of preparation methods of ternary precursor material, include the following steps: S1, nickel source, cobalt source and manganese source are weighed according to scheduled ratio and are dissolved in deionized water form the first mixed solution;S2, the first mixed solution, the first strong base solution and complexing agent are added in first reactor;The crystal seed reacted in S2 is added in the second reactor S3, and then the second complexing agent, the second mixed solution and the second highly basic liquor are added to sufficiently being reacted in the second reactor again;The reaction product sufficiently reacted in S3, is transferred in ageing tank that the reaction was continued by S4, and then sediment therein is transferred in the filter press and is separated by solid-liquid separation, and cleans the sediment with deionized water;S5 will be dried in oxygen-enriched atmosphere in sediment obtained in S4 and be obtained ternary precursor material.The present invention also provides a kind of ternary precursor materials simultaneously.
Description
Technical field
The present invention relates to a kind of lithium ion battery ternary precursor materials and preparation method thereof.
Background technique
Ternary material is stratiform nickel cobalt manganese composite positive pole, and wherein main metal element is nickel, manganese, cobalt metal.With cobalt
Sour lithium, lithium nickelate, LiMn2O4 are compared, and have at low cost, big, good, stable structure of good cycle, thermal stability of discharge capacity etc.
Advantage.Synergistic effect of the ternary material by Ni-Co-MN, the height ratio capacity of the good cycle performance of synthesis cobalt acid lithium, lithium nickelate
The features such as with the high security of LiMn2O4 and low cost, comprehensive performance is better than any single group polymerisable compounds, it has also become most sends out
The anode material for lithium-ion batteries of exhibition prospect.
Ternary precursor material is to prepare ternary material critical materials, and the physical and chemical performance of ternary precursor material directly affects
Ternary material chemical property, directly restriction high-performance ternary material application, including ternary precursor pattern, size distribution, crystalline substance
Body structure etc..The production technology of current ternary precursor material is difficult to control its internal structure.Conventional three-way presoma at present
The ternary material of material preparation is unable to satisfy on-vehicle battery index request.
Summary of the invention
For the problems of the prior art, meet on-vehicle battery index request, structure the object of the present invention is to provide a kind of
Controllable ternary precursor material and preparation method thereof and a kind of ternary material.
A kind of preparation method of ternary precursor material, includes the following steps:
S1, nickel source, cobalt source and manganese source weighed and be dissolved in deionized water according to scheduled ratio form first
Mixed solution, and make the scheduled ratio of molar ratio of nickel ion in first mixed solution, cobalt ions and manganese ion;
S2, the first mixed solution and the first strong base solution are added in first reactor, and the first complexing agent is then added thereto, described
First mixed solution is reacted with the hydroxide ion in first reactor generates crystal seed;S3, described in reaction obtains in S2
Crystal seed is added in second reactor, then again by the second complexing agent, be dissolved in deionized water and formed by nickel source, cobalt source and manganese source
The second mixed solution and the second strong base solution be added to sufficiently reacted in the second reactor and generate have it is heavy
The slurry in shallow lake controls the solid content control of the slurry within preset range;S4, the material that will sufficiently be reacted in S3
Slurry is transferred in ageing tank that the reaction was continued and then is separated by solid-liquid separation, and the precipitating isolated is cleaned with deionized water;S5, will be
Sediment obtained in S4 dries in oxygen-enriched atmosphere and obtains ternary precursor material.
Further, the first reactor and the second reactor are systemic circulation flux reaction kettle.
Further, in step sl, first complexing agent is continuously added to first reactor at a predetermined rate,
And the time of first complexing agent is continuously added between 1-24 hours.
Further, in step s 2, the pH value in the first reactor is between 10.5-12.8, and institute
The reaction temperature in first reactor is stated between 40-80 DEG C.
Further, in step s 2, the partial size of the crystal seed is between 1-9 μm.
Further, in step s3, the solid content in the slurry is between 700-1600g/L.
Further, in step s3, the pH value in the second reactor is between 10.5-12.8.
Further, in step s 5, the drying temperature is between 270-350 DEG C, and drying time was between 1-4 hours
Between.
A kind of ternary precursor material, the molecular formula of the ternary precursor material are NixCoyMnz(OH)2, wherein x+y+
The value range of z=1, x, y, z are 0~1, and x, y, z is not equal to 0 and 1, the ternary material precursor structure spherical in shape,
The spherical structure includes shell, kernel and transition zone, and the shell is compact texture, and the kernel is loose and porous structure,
The transition zone is set between the shell and kernel, and the ternary precursor material is by nickel hydroxide, cobalt hydroxide and hydrogen
The mixture that manganese oxide is mixed to form in atomic level, and the crystallinity of the shell is higher than the crystallinity of the kernel, institute
The crystallinity of transition zone is stated between the shell and the kernel.
Further, the D50 of the ternary precursor material is between 2-18 μm, and (D5+D95): D50≤2.2.
Further, the thickness of the shell is between 0.5-10 μm, the thickness of the transition zone between 0-2 μm it
Between, the diameter of the kernel is not more than 10 μm;And the tap density of the shell is greater than the tap density of the kernel, wherein
The tap density of the shell is not less than 2.5g/cm3, the tap density of the kernel is no more than 3.0g/cm3。
Further, the ratio of the diameter of the diameter and kernel of the ternary precursor shell between 1:1-9:1 it
Between.
Further, the density of the kernel of the ternary precursor is incrementally increased from interior.
Further, the pore size control of the kernel of the ternary precursor is between 0.1-2 μm.
Further, the porosity of the ternary material precursor material controls between 20-70%.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of ternary precursor material provided by the invention.
Fig. 2 is a kind of particle size distribution figure of embodiment of ternary material precursor provided by the invention.
Fig. 3 is a kind of microscopic appearance figure of embodiment of ternary material precursor provided by the invention.
Fig. 4 is the sectional drawing of the ternary precursor material in Fig. 3.
Main element symbol description
Nothing
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Referring to Fig. 1, being the preparation method flow chart of ternary precursor material provided by the invention.The ternary precursor
The preparation method of material includes the following steps:
S1, nickel source, cobalt source and manganese source weighed and be dissolved in deionized water according to scheduled ratio form first
Mixed solution, and the molar concentration of nickel ion in first mixed solution, cobalt ions and manganese ion is scheduled ratio;
The nickel source, cobalt source and manganese source are water-soluble salt.Specifically, the nickel source can be nickel sulfate, nitric acid
The mixture of one or more of nickel and nickel chloride, the cobalt source can be one of cobaltous sulfate, cobalt nitrate and cobalt chloride
Or several mixtures, the manganese source can be the mixture of one or more of manganese sulfate, manganese nitrate and manganese chloride.It is described
The molar ratio of nickel ion described in first mixed solution, cobalt ions and manganese ion can be adjusted accordingly according to actual needs
Whole, the application does not limit this.
First mixed solution and the first strong base solution are added in first reactor, are then added thereto by S2
First complexing agent, first mixed solution is reacted with the hydroxide ion in first reactor generates crystal seed;
In the present embodiment, the first reactor is reaction kettle.Specifically, the first reactor is logical for systemic circulation
Quantitative response kettle, the circulation flux of the reaction kettle of the systemic circulation flux is between 10-40m3Between/h.Further, in this implementation
In mode, the reaction kettle is induction type water conservancy diversion barrel structure.The crystal seed reactor has inside it before mixed solution is added
Suitable bottom liquid.The bottom liquid is blank bottom liquid, for example the bottom liquid can be deionized water.Bottom liquid in the crystal seed reactor
Liquid level it is 10-100cm higher than the height of the feed inlet.In other words, the feed inlet of the crystal seed reactor is located at institute
The liquid level of bottom liquid in crystal seed reactor is stated hereinafter, so as to enable the solution of the addition in the crystal seed reactor quickly to divide
It dissipates.
Specifically, first mixed solution is added in the first reactor, then at a predetermined rate to institute
It states and is continuously added to the first complexing agent in first reactor.In the present embodiment, first complexing agent is ammonium hydroxide, and described
The concentration of ammonium hydroxide is stepped up from 0g/L to 45g/L, and the time for being continuously added to the ammonium hydroxide can control between 1-24 hours.
In other embodiments, first complexing agent can also for ammonium sulfate, EDTA (ethylenediamine tetra-acetic acid), sodium bicarbonate and
At least one of oxalic acid.
First mixed solution is reacted with first strong base solution and the ammonium hydroxide can generate precipitating, and control first is anti-
Answer the pH value of the solidliquid mixture in device between 10.5-12.8.The reaction temperature in the first reactor is controlled simultaneously
Between 40-80 DEG C.
In the present embodiment, the molal quantity of hydroxide ion and first mixed solution in first strong base solution
In the ratio between the molal quantity of metal cation between 0.5-2.8.First strong base solution is sodium hydroxide or hydrogen-oxygen
Change one or both of potassium solution.
In mixed solution, the nickel ion, cobalt ions and manganese ion and first strong base solution and the ammonium hydroxide
Hydroxide ion combines the mixture for generating nickel hydroxide, cobalt hydroxide and manganous hydroxide.The crystal seed is by the mixing
The particle that object is formed, the partial size of the crystal seed is between 1-9 μ-.
The crystal seed reacted in S2 is added in the second reactor S3, then again by the second complexing agent,
Second mixed solution and the second highly basic liquor are added to sufficiently being reacted in the second reactor and generated with solid
The slurry of precipitating controls the solid content of the slurry within preset range;
In the present embodiment, the second reactor is similarly the reaction kettle of systemic circulation flux, and is similarly induction
Formula water conservancy diversion barrel structure.In specific reaction process, after the crystal seed is added into the second reactor, then it is added thereto
Second complexing agent simultaneously controls the second complexing agent concentration in the second reactor, then again successively by second mixed solution
It is added in the second reactor and is reacted with the second highly basic liquor, generate the slurry with precipitating at this time.The precipitating
Be by the crystal seed that is formed in step s 2 it is core, and continues to grow up to be formed in the second reactor.
In the present embodiment, second mixed solution is equally by the nickel source, cobalt source and manganese source according to predetermined weighing
And it is dissolved in the water and to be formed.The type of the nickel source, cobalt source and manganese source can be with the nickel source in first mixed liquor, cobalt
Source is identical with the type of manganese source, can not also be identical, and which is not limited by the present invention;In addition, in second mixed solution
The molar concentration of nickel ion, cobalt ions and manganese ion can with nickel ion, cobalt ions and the manganese in first mixed solution from
The molar concentration of son is identical, naturally it is also possible to which not identical, which is not limited by the present invention.
Second complexing agent can be at least one of ammonium hydroxide, ammonium sulfate, EDTA, sodium bicarbonate and oxalic acid.It can be with
Understand, second complexing agent can be identical as first complexing agent, can not also be identical.In this application, described second
Complexing agent is ammonium hydroxide.The ammonia concn is between 1.0-20.0%.The ammonium hydroxide is connected at a predetermined rate by metering pump
It is continuous to be added in the second reactor.Certainly, second complexing agent can also be the complexing agent of other types, the present invention couple
This is without limitation.
Cation mole concentration in second mixed solution is between 0.5-2.8mol/L, in the second mixed solution
Metal cation molal quantity and the ratio between the molal quantity of metal cation in first mixed solution between 0.4-1.5 it
Between.
The pH value of reaction environment is controlled in step s3 between 10.5-12.8.Institute in second mixed solution
Stating nickel source, cobalt source and manganese source can be identical as the type of the nickel source, cobalt source and manganese source in first mixed solution, certainly
Can not also be identical, the application is without limitation.The nickel ion, cobalt ions and manganese ion in second mixed solution
Molar ratio can be adjusted correspondingly according to actual needs, which is not limited by the present invention.
The solid content in the slurry is controlled in such a way that filtering returns in the present embodiment.Specifically, passed through
The mode that filter returns controls the solid content in the slurry between 700-1600g/L, and filters the time control of return
Between 1-12h.Precipitating therein is filtered out and returned in the second reactor by filtering, then will filtered out
Liquid exhausts.
The reaction product sufficiently reacted in S3 is transferred in ageing tank that the reaction was continued and then carries out solid-liquid point by S4
From, and the sediment isolated is cleaned with deionized water;
The reaction product obtained in previous step is transferred in ageing tank, and adjust institute by the way that third lye solution is added
The pH value in ageing tank is stated between 10-13, at the same by stirring make the complete nickel ion of unreacted in solution, cobalt ions or
Manganese ion sufficiently reacts generation precipitating with the hydroxide ion in reaction environment.Solid precipitation and separation in the ageing tank is gone out
Come, that is, is separated by solid-liquid separation.In addition, in the ageing tank carry out the reaction was continued can to it is described precipitating be surface modified,
So as to improve the performance of final acquired product.Specifically, in this application, using by the precipitating and liquid in ageing tank
It is transferred in plate and frame filter press and is separated by solid-liquid separation, to isolate solid precipitating therein.Then the precipitating isolated is used
Deionized water is washed to pH value less than 8.
The third lye solution is similarly one or both of sodium hydroxide or potassium hydroxide solution.
S5 will be dried in oxygen-enriched atmosphere in sediment obtained in S4 and be obtained ternary precursor material.
In this application, the sediment is the nickel hydroxide, cobalt hydroxide, manganous hydroxide formation atomic level mixing
Mixture.It is to be dried in the rotary kiln of oxygen-enriched atmosphere by the sediment, wherein drying temperature is between 270-350 DEG C
Between, drying time is between 1-4 hours.The porosity of the ternary precursor material controls between 20-70%, and
The porosity of the ternary precursor material can be adjusted correspondingly by adjusting the thickness ratio of shell and kernel.It is described
The aperture of the kernel of ternary precursor material is can be controlled between 0.1-2 μm.
Fig. 2-Fig. 4 is please referred to, the molecular formula of the ternary precursor material is NixCoyMnz(OH)2, wherein x+y+z
The value range of=1, x, y, z are 0~1, and x, y, z is not equal to 0 and 1.The ternary precursor material is globoid structure,
It includes shell, transition zone and the kernel surrounded by the shell.The shell is compact texture, and the kernel is loose porous
Structure, the transition zone is between the shell and the kernel.It is appreciated that the shell, the transition zone and described
The tap density of kernel is different, and the tap density of the shell is greater than the tap density of the kernel, the jolt ramming of the transition zone
Density is less than the tap density of the shell and is greater than the tap density of the kernel.It is appreciated that the crystallinity of the shell
Higher than the crystallinity of the transition zone, and the crystallinity of the transition zone is greater than the crystallinity of the kernel.The shell
Thickness is between 0.5-10 μm, and the density of the shell is not less than 2.5g/cm3.Certainly, the diameter of the shell and vibration
Real density can be adjusted according to actual needs, and the utility model does not limit this.In addition, the ternary precursor material
Interior nuclear diameter be not more than 10 μm, and density be not more than 3.0g/cm3.The thickness of the transition zone is between 0-2 μm.
In addition, the ratio of the diameter of the diameter of the ternary precursor material envelope and the kernel between 1:1-1:9 it
Between.The density of the kernel of the ternary precursor material is incrementally increased from interior.Specifically, the density of the kernel is in
Stratiform densification gradient distribution, and the stratiform densification gradient of the kernel is between 2.0-4.2g/cm3Between.
The partial size of the ternary precursor material is between 1-40 μm.Further, the ternary precursor material
D50 is between 2-18 μm, and (D5+D95): D50≤2.2.Wherein the D50 refer to ordinate cumulative distribution 50% pair
The diameter value for the abscissa answered.Likewise, the D5 refers to the diameter value of abscissa corresponding to ordinate cumulative distribution 5%,
The D95 refers to the diameter value of abscissa corresponding to ordinate cumulative distribution 95%.
The application also provides a kind of ternary material, and the ternary material is mixed by the ternary precursor material and lithium source
And it is sintered and is prepared under pure oxygen or air atmosphere with 700-1200 DEG C.The lithium source is lithium hydroxide, lithium nitrate, sulphur
One of sour lithium, lithium chloride, lithium fluoride, lithium carbonate and lithium oxalate are several.The ternary material can adulterate Al,
At least one of at least one of Ca, Na, Ti, Mg, Zr and W metal cation, or doping S, Cl and F anion.
After the ternary material is assembled into battery, capacity retention ratio is not small after carrying out charge and discharge 2000 weeks under 20C multiplying power
In 88%, there is good high rate performance.
The preparation method of ternary precursor material disclosed herein can control the ternary precursor material of the preparation
Pattern and partial size, and this method is simply controllable, is suitble to industrialized production.In addition, the ternary precursor material in the application
Shell and kernel Crystal it is different, the ternary material using ternary precursor material preparation has preferable multiplying power
Performance and good stable circulation performance are suitable as vehicle mounted dynamic battery use.
Embodiment one
Nickel source, cobalt source and manganese source are weighed according to scheduled ratio and be dissolved in deionized water formed first mixing it is molten
Liquid.And the ratio between molar concentration of nickel ion described in first mixed solution, cobalt ions and manganese ion is 5/2/3.
First mixed solution is added in first reactor, and the first reactor is reaction kettle and circulation flux is
25m3/h.Then ammonium hydroxide and the first strong base solution are added with constant rate of speed thereto, the concentration of the ammonium hydroxide from 0g/L gradually
It is increased to 30g/L, the duration that the ammonium hydroxide is added is 12 hours;Mole of hydroxide ion in first strong base solution
Several the ratio between molal quantitys of cation with first mixed solution are 0.5, and first strong base solution is that sodium hydroxide is molten
Liquid.
The reaction temperature for controlling the reaction environment in first reactor is 60 DEG C.At this time first mixed solution with react
Hydroxyl reaction in environment can generate precipitating, and the precipitating is crystal seed.The partial size of the crystal seed is between 1-7 μm.
The crystal seed obtained in previous step reaction is added in second reactor, then again by the second complexing agent, the
Two mixed solutions and the second strong base solution are added to sufficiently being reacted in the second reactor and generated and precipitate with solid
Slurry.The second reactor is similarly systemic circulation flux reaction kettle, and recycling flux is 25m3/h.Second complexing
Agent is ammonium hydroxide;Second strong base solution is sodium hydroxide solution, and molal quantity cationic in second mixed solution
It is 1 with the ratio between molal quantity of hydroxide ion in second strong base solution.
Second mixed solution, which is equally dissolved in deionized water by nickel nitrate, cobalt nitrate and manganese nitrate, to be obtained, and
The ratio between molar concentration of the nickel ion, the cobalt ions and the manganese ion is 5/2/3.The second container is in reaction process
In pH value be between 10.5-12.8, and use filtering return mode control the solid content of the slurry as 1000g/
L;
The reaction product sufficiently reacted in previous step is transferred in ageing tank to the reaction was continued and controls in ageing tank
PH value be 10, then by ageing tank precipitating and liquid move in the filter press and be separated by solid-liquid separation, and use deionization
Water washs the sediment to pH value less than 8.
Ternary forerunner will be obtained within drying and processing 3 hours with 300 DEG C in oxygen-enriched atmosphere in sediment obtained in previous step
Body material.The D50 of the presoma of obtained ternary material is 16 μm.
Embodiment two
Nickel source, cobalt source and manganese source are weighed according to scheduled ratio and be dissolved in deionized water formed first mixing it is molten
Liquid.And the ratio between molar concentration of nickel ion described in first mixed solution, cobalt ions and manganese ion is 3/3/3.
First mixed solution is added in first reactor, and the first reactor is reaction kettle and circulation flux is
15m3/h.Then ammonium hydroxide and the first strong base solution are added with constant rate of speed thereto, the concentration of the ammonium hydroxide from 0g/L gradually
It is increased to 15g/L, the duration that the ammonium hydroxide is added is 24 hours;Mole of hydroxide ion in first strong base solution
Several the ratio between molal quantitys of cation with first mixed solution are 1, and first strong base solution is sodium hydroxide solution.
The reaction temperature for controlling the reaction environment in reaction kettle is 40 DEG C.First mixed solution and reaction environment at this time
In hydroxyl reaction can generate precipitating, the precipitating as crystal seed.The partial size of the crystal seed is between 3-9 μm.
The crystal seed obtained in reacting in previous step is added in second reactor, then again by ammonium hydroxide, the second mixing
Solution and sodium hydroxide solution are added to sufficiently being reacted in the second reactor and generate the slurry with solid precipitating.
The second reactor is similarly systemic circulation flux reaction kettle, and recycling flux is 15m3/h.Second complexing agent is ammonia
Water;Second strong base solution be sodium hydroxide solution, and molal quantity cationic in second mixed solution with it is described
The ratio between molal quantity of hydroxide ion is 1.5 in second strong base solution.
Second mixed solution is equally dissolved in deionized water and is obtained by nickel sulfate, cobaltous sulfate and manganese manganese sulfate, and
And the ratio between molar concentration of the nickel ion, the cobalt ions and the manganese ion is 3/3/3.The second container was reacting
PH value in journey is between 11-12, and the mode for using filtering to return controls the solid content of the slurry as 700g/L;
The reaction product sufficiently reacted in previous step is transferred in ageing tank to the reaction was continued and controls in ageing tank
PH value be 11, then by ageing tank precipitating and liquid move in the filter press and be separated by solid-liquid separation, and use deionization
Water washs the sediment to pH value less than 8.
Ternary forerunner will be obtained within drying and processing 3 hours with 330 DEG C in oxygen-enriched atmosphere in sediment obtained in previous step
Body material.The D50 of the presoma of obtained ternary material is 2 μm.
Embodiment three
Nickel source, cobalt source and manganese source are weighed according to scheduled ratio and be dissolved in deionized water formed first mixing it is molten
Liquid.And the ratio between molar concentration of nickel ion described in first mixed solution, cobalt ions and manganese ion is 8/1/1.
First mixed solution is added in first reactor, and the first reactor is reaction kettle and circulation flux is
40m3/h.Then ammonium hydroxide and the first strong base solution are added with constant rate of speed thereto, the concentration of the ammonium hydroxide from 0g/L gradually
It is increased to 45g/L, the duration that the ammonium hydroxide is added is 1 hour;Mole of hydroxide ion in first strong base solution
Several the ratio between molal quantitys of cation with first mixed solution are 1.5, and first strong base solution is that sodium hydroxide is molten
Liquid.
The reaction temperature for controlling the reaction environment in the first reactor is 80 DEG C.At this time first mixed solution with
Hydroxyl reaction in reaction environment can generate precipitating, and the precipitating is crystal seed.The partial size of the crystal seed between 1-9 μm it
Between.
The crystal seed obtained in previous step reaction is added in second reactor, then again by the second complexing agent, the
Two mixed solutions and the second strong base solution are added to sufficiently being reacted in the second reactor and generated and precipitate with solid
Slurry.The second reactor is similarly systemic circulation flux reaction kettle, and recycling flux is 40m3/h.Second complexing
Agent is ammonium hydroxide;Second strong base solution is sodium hydroxide solution, and molal quantity cationic in second mixed solution
It is 1 with the ratio between molal quantity of hydroxide ion in second strong base solution.
Second mixed solution, which is equally dissolved in deionized water by nickel chloride, cobalt chloride and manganese chloride, to be obtained, and
The ratio between molar concentration of the nickel ion, the cobalt ions and the manganese ion is 8/1/1.The second container is in reaction process
In pH value between 10.5-11.5, and use filtering return mode control the solid content of the slurry as 1600g/L;
The reaction product sufficiently reacted in previous step is transferred in ageing tank to the reaction was continued and controls in ageing tank
PH value be 13, then by ageing tank precipitating and liquid move in the filter press and be separated by solid-liquid separation, and use deionization
Water washs the sediment to pH value less than 8.
Ternary forerunner will be obtained within drying and processing 3 hours with 350 DEG C in oxygen-enriched atmosphere in sediment obtained in previous step
Body material.The D50 of the presoma of obtained ternary material is 18 μm.
Example IV
Nickel source, cobalt source and manganese source are weighed according to scheduled ratio and be dissolved in deionized water formed first mixing it is molten
Liquid.And the ratio between molar concentration of nickel ion described in first mixed solution, cobalt ions and manganese ion is 8/1/1.
First mixed solution is added in first reactor, and the first reactor is reaction kettle and circulation flux is
30m3/h.Then ammonium hydroxide and the first strong base solution are added with constant rate of speed thereto, the concentration of the ammonium hydroxide from 0g/L gradually
It is increased to 40g/L, the duration that the ammonium hydroxide is added is 5 hours;Mole of hydroxide ion in first strong base solution
Several the ratio between molal quantitys of cation with first mixed solution are 0.5, and first strong base solution is that sodium hydroxide is molten
Liquid.
The pH value for controlling the reaction environment in the first reactor is 12, while being controlled anti-in the first reactor
The reaction temperature for answering environment is 70 DEG C.At this time first mixed solution reacted with the hydroxyl in reaction environment can generate it is heavy
It forms sediment, the precipitating is crystal seed.The partial size of the crystal seed is between 5-9 μm.
The crystal seed obtained in previous step reaction is added in second reactor, then again by the second complexing agent, the
Two mixed solutions and the second strong base solution are added to sufficiently being reacted in the second reactor and generated and precipitate with solid
Slurry.The second reactor is similarly systemic circulation flux reaction kettle, and recycling flux is 30m3/h.Second complexing
Agent is ammonium hydroxide;Second strong base solution is sodium hydroxide solution, and molal quantity cationic in second mixed solution
It is 0.8 with the ratio between molal quantity of hydroxide ion in second strong base solution.
Second mixed solution is equally dissolved in deionized water and is obtained by nickel sulfate, cobaltous sulfate and manganese manganese sulfate, and
And the molar concentration of the nickel ion, the cobalt ions and the manganese ion is only than being 8/1/1.The second container was reacting
PH value in journey is between 11.5-12.8, and the mode for using filtering to return controls the solid content of the slurry as 1200g/
L;
The reaction product sufficiently reacted in previous step is transferred in ageing tank to the reaction was continued and controls in ageing tank
PH value be 12, then by ageing tank precipitating and liquid move in the filter press and be separated by solid-liquid separation, and use deionization
Water washs the sediment to pH value less than 8.
Ternary forerunner will be obtained within drying and processing 3 hours with 300 DEG C in oxygen-enriched atmosphere in sediment obtained in previous step
Body material.The D50 of the presoma of obtained ternary material is 15 μm.
Embodiment five
Nickel source, cobalt source and manganese source are weighed according to scheduled ratio and be dissolved in deionized water formed first mixing it is molten
Liquid.And the ratio between molar concentration of nickel ion described in first mixed solution, cobalt ions and manganese ion is 6/2/2.
First mixed solution is added in the reaction kettle, and the first reactor is reaction kettle and circulation flux is
25m3/h.Then ammonium hydroxide and the first strong base solution are added with constant rate of speed thereto, the concentration of the ammonium hydroxide from 0g/L gradually
It is increased to 20g/L, the duration that the ammonium hydroxide is added is 20 hours;Mole of hydroxide ion in first strong base solution
Several the ratio between molal quantitys of cation with first mixed solution are 0.5, and first strong base solution is that sodium hydroxide is molten
Liquid.
The reaction temperature for controlling the reaction environment in the first reactor is 70 DEG C.At this time first mixed solution with
Hydroxyl reaction in reaction environment can generate precipitating, and the precipitating is crystal seed.The partial size of the crystal seed between 1-9 μm it
Between.
The crystal seed obtained in previous step reaction is added in second reactor, then again by the second complexing agent, the
Two mixed solutions and the second strong base solution are added to sufficiently being reacted in the second reactor and generated and precipitate with solid
Slurry.The second reactor is similarly systemic circulation flux reaction kettle, and recycling flux is 30m3/h.Second complexing
Agent is ammonium hydroxide;Second strong base solution is sodium hydroxide solution, and molal quantity cationic in second mixed solution
It is 1.5 with the ratio between molal quantity of hydroxide ion in second strong base solution.
Second mixed solution is equally dissolved in deionized water and is obtained by nickel sulfate, cobaltous sulfate and manganese manganese sulfate, and
And the ratio between molar concentration of the nickel ion, the cobalt ions and the manganese ion is 6/2/2.The second container was reacting
PH value in journey is between 12-12.8, and the mode for using filtering to return controls the solid content of the slurry as 900g/L;
The reaction product sufficiently reacted in previous step is transferred in ageing tank to the reaction was continued and controls in ageing tank
PH value be 12.5, then by ageing tank precipitating and liquid move in the filter press and be separated by solid-liquid separation, and spend from
Sub- water washs the sediment to pH value less than 8.
Ternary forerunner will be obtained within drying and processing 3 hours with 270 DEG C in oxygen-enriched atmosphere in sediment obtained in previous step
Body material.The D50 of the presoma of obtained ternary material is 8 μm.
Embodiment six
Nickel source, cobalt source and manganese source are weighed according to scheduled ratio and be dissolved in deionized water formed first mixing it is molten
Liquid.And the ratio between molar concentration of nickel ion described in first mixed solution, cobalt ions and manganese ion is 4/4/2.
First mixed solution is added in the reaction kettle, and the first reactor is reaction kettle and circulation flux is
25m3/h.Then ammonium hydroxide and the first strong base solution are added with constant rate of speed thereto, the concentration of the ammonium hydroxide from 0g/L gradually
It is increased to 20g/L, the duration that the ammonium hydroxide is added is 20 hours;Mole of hydroxide ion in first strong base solution
Several the ratio between molal quantitys of cation with first mixed solution are 0.5, and first strong base solution is that sodium hydroxide is molten
Liquid.
The reaction temperature for controlling the reaction environment in the first reactor is 70 DEG C.At this time first mixed solution with
Hydroxyl reaction in reaction environment can generate precipitating, and the precipitating is crystal seed.The partial size of the crystal seed between 1-9 μm it
Between.
The crystal seed obtained in previous step reaction is added in second reactor, then again by the second complexing agent, the
Two mixed solutions and the second strong base solution are added to sufficiently being reacted in the second reactor and generated and precipitate with solid
Slurry.The second reactor is similarly systemic circulation flux reaction kettle, and recycling flux is 30m3/h.Second complexing
Agent is ammonium hydroxide;Second strong base solution is sodium hydroxide solution, and molal quantity cationic in second mixed solution
It is 1.5 with the ratio between molal quantity of hydroxide ion in second strong base solution.
Second mixed solution is equally dissolved in deionized water and is obtained by nickel sulfate, cobaltous sulfate and manganese manganese sulfate, and
And the ratio between molar concentration of the nickel ion, the cobalt ions and the manganese ion is 6/2/2.The second container was reacting
PH value in journey is between 12-12.8, and the mode for using filtering to return controls the solid content of the slurry as 900g/L;
The reaction product sufficiently reacted in previous step is transferred in ageing tank to the reaction was continued and controls in ageing tank
PH value be 12.5, then by ageing tank precipitating and liquid move in the filter press and be separated by solid-liquid separation, and spend from
Sub- water washs the sediment to pH value less than 8.
Ternary forerunner will be obtained within drying and processing 3 hours with 270 DEG C in oxygen-enriched atmosphere in sediment obtained in previous step
Body material.The D50 of the presoma of obtained ternary material is 8 μm.
Claims (15)
1. a kind of preparation method of ternary precursor material, includes the following steps:
Nickel source, cobalt source and manganese source are weighed according to scheduled ratio and are dissolved in the first mixing of formation in deionized water by S1
Solution, and make the scheduled ratio of molar ratio of nickel ion in first mixed solution, cobalt ions and manganese ion;
S2, the first mixed solution and the first strong base solution are added in first reactor, and the first complexing agent is then added thereto,
First mixed solution is reacted with the hydroxide ion in first reactor generates crystal seed;
S3, by the crystal seed reacted in S2 be added second reactor in, then again by the second complexing agent, by nickel source,
Cobalt source and manganese source are dissolved in the second mixed solution formed in deionized water and the second strong base solution is added to described second instead
Answer and the slurry with precipitating sufficiently reacted and generated in device, control the slurry solid content control preset range it
It is interior;
The slurry sufficiently reacted in S3 is transferred in ageing tank that the reaction was continued and then is separated by solid-liquid separation by S4, and
The precipitating isolated is cleaned with deionized water;
S5 will be dried in oxygen-enriched atmosphere in sediment obtained in S4 and be obtained ternary precursor material.
2. the preparation method of ternary precursor material according to claim 1, which is characterized in that the first reactor and
The second reactor is systemic circulation flux reaction kettle.
3. the preparation method of ternary precursor material according to claim 2, which is characterized in that in step sl, described
First complexing agent is continuously added to first reactor at a predetermined rate, and is continuously added to the time of first complexing agent
Between 1-24 hours.
4. the preparation method of ternary precursor material according to claim 1, which is characterized in that in step s 2, described
PH value in first reactor is between 10.5-12.8, and the reaction temperature in the first reactor is between 40-80
Between DEG C.
5. the preparation method of ternary precursor material according to claim 1, which is characterized in that in step s 2, described
The partial size of crystal seed is between 1-9 μm.
6. the preparation method of ternary precursor material according to claim 1, which is characterized in that in step s3, described
Solid content in slurry is between 700-1600g/L.
7. the preparation method of ternary precursor material according to claim 1, which is characterized in that in step s3, described
PH value in second reactor is between 10.5-12.8.
8. the preparation method of ternary precursor material according to claim 1, which is characterized in that in step s 5, described
Drying temperature is between 270-350 DEG C, and drying time is between 1-4 hours.
9. a kind of ternary precursor material, which is characterized in that the molecular formula of the ternary precursor material is NixCoyMnz(OH)2,
The value range of wherein x+y+z=1, x, y, z are 0~1, and x, y, z is not equal to 0 and 1, and the ternary material precursor is in ball
Shape structure, the spherical structure include shell, kernel and transition zone, and the shell is compact texture, and the kernel is loose more
Pore structure, the transition zone are set between the shell and kernel, and the ternary precursor material is by nickel hydroxide, hydroxide
The mixture that cobalt and manganous hydroxide are mixed to form in atomic level, and the crystallinity of the shell is higher than the crystallization of the kernel
Degree, the crystallinity of the transition zone is between the shell and the kernel.
10. ternary precursor material according to claim 9, which is characterized in that the D50 of the ternary precursor material is situated between
Between 2-18 μm, and (D5+D95): D50≤2.2.
11. ternary precursor material according to claim 9, which is characterized in that the thickness of the shell is between 0.5-10 μ
Between m, for the thickness of the transition zone between 0-2 μm, the diameter of the kernel is not more than 10 μm;And the vibration of the shell
Real density is greater than the tap density of the kernel, wherein the tap density of the shell is not less than 2.5g/cm3, the kernel
Tap density is not more than 3.0g/cm3。
12. ternary precursor material according to claim 9, which is characterized in that the diameter of the ternary precursor shell
Ratio with the diameter of the kernel is between 1:1-9:1.
13. ternary precursor material according to claim 9, which is characterized in that the kernel of the ternary precursor it is close
Degree is incrementally increased from interior.
14. ternary precursor material according to claim 9, which is characterized in that the hole of the kernel of the ternary precursor
Diameter controls between 0.1-2 μm.
15. ternary precursor material according to claim 9, which is characterized in that the ternary material precursor material
Porosity controls between 20-70%.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005267956A (en) * | 2004-03-17 | 2005-09-29 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary battery and positive electrode material therefor |
CN102092798A (en) * | 2010-12-01 | 2011-06-15 | 兰州金川新材料科技股份有限公司 | Method for continuously synthesizing precursor of lithium ion battery positive material |
CN104347866A (en) * | 2013-07-26 | 2015-02-11 | 比亚迪股份有限公司 | Lithium battery cathode material and preparation method thereof |
CN105399154A (en) * | 2015-11-25 | 2016-03-16 | 兰州金川新材料科技股份有限公司 | Method for producing Ni-Co-Mn ternary hydroxide |
CN107069023A (en) * | 2017-03-30 | 2017-08-18 | 合肥工业大学 | A kind of preparation method of hollow-core construction lithium ion battery electrode material |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3842348B2 (en) * | 1996-09-02 | 2006-11-08 | 日本化学工業株式会社 | Method for producing Ni-Mn composite hydroxide |
US20020053663A1 (en) * | 2000-11-06 | 2002-05-09 | Tanaka Chemical Corporation | High density cobalt-manganese coprecipitated nickel hydroxide and process for its production |
JP5730676B2 (en) * | 2011-06-06 | 2015-06-10 | 住友金属鉱山株式会社 | Cathode active material for non-aqueous electrolyte secondary battery and method for producing the same, and nickel cobalt manganese composite hydroxide and method for producing the same |
KR101429531B1 (en) * | 2012-01-05 | 2014-08-14 | 한국교통대학교산학협력단 | Precursor for cathode active materials for lithiumsecondary battery with coreshell, cathode active materials and lithiumsecondary battery using the same, and preparation method thereof |
KR101564009B1 (en) * | 2014-02-13 | 2015-10-28 | 주식회사 이엔드디 | Continuously preparing method for Ni-Co-Mn composite precursor using Couette-Taylor vortix reactor |
JP6603058B2 (en) * | 2014-08-20 | 2019-11-06 | 住友化学株式会社 | Method for producing lithium-containing composite oxide and lithium-containing composite oxide |
CN104852038B (en) | 2015-04-08 | 2017-02-01 | 中国科学院长春应用化学研究所 | Preparation method of high-capacity quickly-chargeable/dischargeable lithium ion battery ternary anode material |
US10790509B2 (en) | 2016-01-06 | 2020-09-29 | Sumitomo Metal Mining Co., Ltd. | Positive-electrode active material precursor for nonaqueous electrolyte secondary battery, positive-electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing positive-electrode active material precursor for nonaqueous electrolyte secondary battery, and method for manufacturing positive-electrode active material for nonaqueous electrolyte secondary battery |
JP2017168198A (en) * | 2016-03-14 | 2017-09-21 | トヨタ自動車株式会社 | Method for manufacturing positive electrode active material |
CN107240712A (en) * | 2016-03-28 | 2017-10-10 | 赵孝连 | Lithium ion battery oxidative grafting presoma, positive electrode and its preparation method and application |
-
2017
- 2017-11-28 WO PCT/CN2017/113324 patent/WO2019104473A1/en unknown
- 2017-11-28 CN CN201780035059.6A patent/CN109311698B/en active Active
- 2017-11-28 JP JP2019532969A patent/JP7050071B2/en active Active
- 2017-11-28 EP EP17928103.5A patent/EP3719885A4/en active Pending
- 2017-11-28 KR KR1020197020133A patent/KR102283095B1/en active IP Right Grant
-
2019
- 2019-07-08 US US16/504,537 patent/US11440811B2/en active Active
-
2022
- 2022-08-05 US US17/882,000 patent/US20220371913A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005267956A (en) * | 2004-03-17 | 2005-09-29 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary battery and positive electrode material therefor |
CN102092798A (en) * | 2010-12-01 | 2011-06-15 | 兰州金川新材料科技股份有限公司 | Method for continuously synthesizing precursor of lithium ion battery positive material |
CN104347866A (en) * | 2013-07-26 | 2015-02-11 | 比亚迪股份有限公司 | Lithium battery cathode material and preparation method thereof |
CN105399154A (en) * | 2015-11-25 | 2016-03-16 | 兰州金川新材料科技股份有限公司 | Method for producing Ni-Co-Mn ternary hydroxide |
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WO2019104473A1 (en) | 2019-06-06 |
KR102283095B1 (en) | 2021-07-29 |
US20220371913A1 (en) | 2022-11-24 |
KR20190092536A (en) | 2019-08-07 |
US20190359497A1 (en) | 2019-11-28 |
JP2020503229A (en) | 2020-01-30 |
EP3719885A1 (en) | 2020-10-07 |
CN109311698B (en) | 2020-09-04 |
US11440811B2 (en) | 2022-09-13 |
JP7050071B2 (en) | 2022-04-07 |
EP3719885A4 (en) | 2021-08-18 |
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